CN111804704B - Method for treating tetrachloro sodium aluminate solid slag - Google Patents
Method for treating tetrachloro sodium aluminate solid slag Download PDFInfo
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- CN111804704B CN111804704B CN202010679799.7A CN202010679799A CN111804704B CN 111804704 B CN111804704 B CN 111804704B CN 202010679799 A CN202010679799 A CN 202010679799A CN 111804704 B CN111804704 B CN 111804704B
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- polymerization reaction
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- solid slag
- chloride
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- 238000000034 method Methods 0.000 title claims abstract description 97
- 239000007787 solid Substances 0.000 title claims abstract description 90
- 239000002893 slag Substances 0.000 title claims abstract description 55
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001388 sodium aluminate Inorganic materials 0.000 title claims abstract description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 90
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 47
- 239000011780 sodium chloride Substances 0.000 claims abstract description 45
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 35
- 230000005593 dissociations Effects 0.000 claims abstract description 35
- 239000012263 liquid product Substances 0.000 claims abstract description 33
- 239000012452 mother liquor Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
- -1 sodium tetrachloroaluminate Chemical compound 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims description 47
- 230000008025 crystallization Effects 0.000 claims description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002518 antifoaming agent Substances 0.000 claims description 24
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 18
- 239000007800 oxidant agent Substances 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 17
- 230000001590 oxidative effect Effects 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 229920002545 silicone oil Polymers 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000013530 defoamer Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000003672 processing method Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 239000002585 base Substances 0.000 claims 1
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052593 corundum Inorganic materials 0.000 abstract description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 11
- 239000002910 solid waste Substances 0.000 abstract description 8
- 238000012864 cross contamination Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 43
- 239000000047 product Substances 0.000 description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- ONRKUGHFZWYUJP-UHFFFAOYSA-N methylphosphane dihydrochloride Chemical compound Cl.Cl.PC ONRKUGHFZWYUJP-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012267 brine Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 6
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 229960002163 hydrogen peroxide Drugs 0.000 description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for treating tetrachloro sodium aluminate solid slag, which comprises the steps of mixing tetrachloro sodium aluminate solid slag with water for dissociation, adding alkali for polymerization reaction, concentrating, crystallizing and carrying out solid-liquid separation to obtain sodium chloride solid and sodium chlorideConcentrating the mother liquor, and curing the obtained concentrated mother liquor to obtain a liquid product of the polymerized aluminum chloride. The treatment method provided by the invention fully recovers aluminum chloride and sodium chloride obtained by dissociation of sodium tetrachloroaluminate solid slag, not only solves the problem of solid waste disposal, but also prepares a high value-added polyaluminum chloride liquid product, namely Al2O3The mass fraction is more than or equal to 10 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB 15892-2009 are met; the treatment method does not need to introduce an organic solvent, does not have cross contamination, can reduce the cost, and has the advantages of simple process flow, simple and convenient operation, less equipment investment and the like.
Description
Technical Field
The invention relates to the technical field of inorganic chemistry, in particular to a method for treating tetrachloro sodium aluminate solid slag.
Background
The methyl phosphine dichloride is an important organic chemical intermediate, is widely applied to the fields of pesticides, medicines, synthetic materials and the like, and particularly is an intermediate for synthesizing diethyl methylphosphonite. At present, the industrial synthesis method of diethyl methylphosphonite mainly comprises the following three methods: the first method is a synthetic method which takes phosphorus trichloride and triethyl phosphite as raw materials; a second method, which is a synthesis method taking aluminum powder, chloromethane, phosphorus trichloride, ethanol and the like as starting materials; and the third method is a synthesis method which takes aluminum trichloride, chloromethane, phosphorus trichloride, ethanol and the like as starting materials. Among them, the second and third methods often generate a large amount of solid waste after the methyl phosphine dichloride intermediate is distilled, the main component of the solid waste is sodium tetrachloroaluminate, and the solid waste also contains a small amount of impurities such as organic aluminum, organic phosphine and the like. Because sodium tetrachloroaluminate is easily dissolved in water, the generated solid waste is often dissolved in water and then directly discharged, which not only causes great pollution to the environment, but also causes resource waste, and a reasonable and effective treatment method needs to be developed urgently.
CN104445323A discloses a preparation method of an activated alumina porous adsorption material, which comprises the following steps: firstly, dissolving solid sodium tetrachloroaluminate with excessive ethanol water solution for hydrolysis, and filtering to recover insoluble sodium chloride; adding a proper amount of water into the filtrate to obtain ethanol-insoluble aluminum trichloride hexahydrate; then, sequentially adding ammonia water into the aluminum trichloride hexahydrate for reaction, aging, gelling, roasting and the like to obtain the active alumina porous adsorption material. The preparation method has complex process and higher operation difficulty, uses a large amount of organic solvent, and is not suitable for large-scale popularization.
CN105217667A discloses a process for recycling sodium tetrachloroaluminate in glufosinate-ammonium production, which comprises the following steps: firstly, adding a mixture of alcohol and ether into sodium tetrachloroaluminate to serve as a decomposition agent, separating out sodium chloride obtained by decomposition, and dissolving aluminum trichloride obtained by decomposition into a mixture; filtering to obtain sodium chloride solid, and cooling the filtrate to separate out aluminum trichloride solid; the aluminum trichloride is recycled after being purified to reach the raw material standard and is used for synthesizing the methyl phosphine dichloride, and the aluminum trichloride with the reduced complexing ability is added with sodium hydroxide to synthesize the polyaluminum chloride. The process not only can not separate sodium chloride from aluminum chloride completely, but also uses various organic solvents, is easy to cause cross contamination, has energy-consuming operations of heating, cooling and the like, and has high treatment cost.
CN108238621A discloses a method for producing polyaluminium chloride by using a by-product of producing diethyl methylphosphonite, which comprises: slowly adding the byproduct sodium tetrachloroaluminate into a dissolving kettle for dissolving, then carrying out solid-liquid separation to obtain sodium chloride crystals, and collecting the solution; and adding the collected solution into a reaction kettle, and sequentially adding ferric trichloride, hydrochloric acid, aluminum hydroxide and calcium metaaluminate to perform polymerization reaction to obtain polyaluminium chloride. The process of dissolving the byproduct sodium tetrachloroaluminate needs a large amount of organic solvent, so that the method has high recovery cost, is easy to cause product cross contamination and is not environment-friendly.
CN105502326A discloses a method for preparing aluminum tripolyphosphate by utilizing methyl phosphorus dichloride production waste, wherein the waste in the method mainly comprises components such as organic aluminum, organic phosphine, sodium aluminate and sodium chloride, phosphoric acid or phosphate is added, condensation reaction is carried out at high temperature of 250-450 ℃, and after the reaction is finished, the aluminum tripolyphosphate product is obtained through washing, drying and micro-crushing. Wherein, the organic components in the waste are taken away by the airflow after high-temperature oxidation, meanwhile, the oxide of aluminum or phosphorus is lighter and can also be taken away along with the airflow, the aim of washing is to remove sodium chloride impurities, and the purity of the aluminum tripolyphosphate in the final product can reach more than 95%. The method does not separate aluminum and sodium before high-temperature reaction, so that a large amount of phosphoric acid or phosphate needs to be added in the high-temperature reaction, the treatment cost is increased, the method belongs to the high-temperature reaction, the energy consumption is high, and the product obtained by the high-temperature reaction is a mixture of sodium phosphate and aluminum tripolyphosphate, and the separation is difficult.
In summary, the treatment methods disclosed in the prior art all have the disadvantages of complex process, high cost, cross contamination risk and the like, and therefore, there is a need to develop an effective treatment method for the tetrachloro sodium aluminate solid slag to achieve the purposes of reducing cost and efficiently and thoroughly utilizing the tetrachloro sodium aluminate solid slag as resources.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for treating tetrachloro sodium aluminate solid slag, which comprises the steps of sequentially adding water to the tetrachloro sodium aluminate solid slag for dissociation and adding alkali for polymerization, then obtaining sodium chloride solid through concentration and crystallization, and curing concentrated mother liquor to obtain a liquid product of the poly aluminum chloride.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a method for treating tetrachloro sodium aluminate solid slag, which comprises the following steps:
(1) mixing the tetrachloro sodium aluminate solid slag with water for dissociation to obtain a dissociation solution;
(2) adding alkali into the dissociation solution obtained in the step (1) to carry out polymerization reaction to obtain a polymerization reaction solution;
(3) concentrating, crystallizing and carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2) to obtain sodium chloride solid and concentrated mother liquor;
(4) curing the concentrated mother liquor obtained in the step (3) to obtain a poly aluminum chloride liquid product.
In the treatment method, after the dissociation of the tetrachloro sodium aluminate solid slag, firstly, alkali is added for the polymerization reaction of aluminum chloride, and insoluble aluminum hydroxide colloid needs to be prevented from being generated in the process; the concentration and crystallization process is strictly controlled, so that the sodium chloride solid and the polyaluminium chloride are completely separated; then curing the concentrated mother liquor to obtain a poly-aluminum chloride liquid product, Al2O3The mass fraction is more than or equal to 10 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB 15892-2009 are met;
the treatment method of the invention can not only further dry the liquid product of the polyaluminum chloride obtained by curing to obtain the solid product of the polyaluminum chloride, Al2O3The mass fraction is more than or equal to 28.0 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB/T22627-2014 are met; or adding ferric trichloride for curing before curing the concentrated mother liquor to obtain a polyaluminum ferric chloride liquid product, Al2O3The mass fraction of the iron is more than or equal to 9 percent, the mass fraction of the total iron (Fe) is more than or equal to 2 percent, the basicity is more than or equal to 60 percent, and the index requirements of the chemical industry standard HG/T5359-2018 are met. Therefore, the person skilled in the art can make a reasonable choice according to the actual situation.
The treatment method provided by the invention fully recovers the aluminum chloride and the sodium chloride obtained by dissociation of the tetrachloro sodium aluminate solid slag, not only solves the problem of disposal of solid waste, but also prepares a polyaluminum chloride product with a high added value, does not need to introduce an organic solvent, does not have cross contamination, can reduce the cost, and has the advantages of simple process flow, simple and convenient operation, less equipment investment and the like.
The invention relates to a production process of tetrachloro sodium aluminate solid slag from diethyl methylphosphonite, in particular to a production process for synthesizing diethyl methylphosphonite by taking phosphorus trichloride, chloromethane, aluminum trichloride, aluminum powder, sodium chloride and the like as raw materials, wherein the tetrachloro sodium aluminate solid slag mainly comprises the following components in percentage by mass: more than or equal to 94 percent of sodium tetrachloroaluminate, less than or equal to 3 percent of sodium chloride, less than or equal to 2 percent of organic phosphine compound and less than or equal to 1 percent of other impurities.
As a preferable technical scheme of the invention, the polyaluminium chloride liquid product in the step (4) is dried to obtain a polyaluminium chloride solid product.
Preferably, the drying is spray drying and/or film evaporation, and the drying treatment is conventional in the art, and can be selected by those skilled in the art according to the actual situation.
Preferably, ferric chloride is added into the concentrated mother liquor obtained in the step (4), and then the aging is carried out to obtain a polyaluminum ferric chloride liquid product.
Preferably, the temperature of the aging is 40 to 100 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the aging time is 24-48 h, such as 24h, 30h, 32h, 36h, 42h or 48h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a preferable technical scheme of the invention, an oxidizing agent is added into the dissociation solution in the step (1) for oxidation.
The oxidant of the invention is used for removing organic impurities in the dissociation solution, including insoluble organic matters in solid residues and soluble macromolecular organic matters, such as phosphorus-containing or aluminum-containing organic impurities like methyl phosphine dichloride. The oxidant can oxidize organic impurities in the dissociation solution into micromolecules from macromolecules and even further oxidize the organic impurities into inorganic matters, so that the oxidized organic impurities can be dissolved in the dissociation solution, and the subsequent treatment is facilitated.
Preferably, the oxidant is any one of, or a combination of at least two of, sodium chlorate, hydrogen peroxide, manganese dioxide, nitric acid, ferric chloride, or ozone, typical but non-limiting examples of such combinations are: a combination of sodium chlorate and hydrogen peroxide, a combination of manganese dioxide and ferric chloride, a combination of hydrogen peroxide and ozone, a combination of sodium chlorate and nitric acid, and the like, and sodium chlorate and/or hydrogen peroxide are preferred.
Preferably, the amount of the oxidizing agent added is 1 to 50% by mass of the solid slag, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%, but is not limited to the recited values, and other values not recited in the above range are also applicable.
As a preferable embodiment of the present invention, an antifoaming agent is added to the polymerization reaction solution in the step (3).
Preferably, the defoamer is any one of or a combination of at least two of a modified silicone oil defoamer, a phosphate ester defoamer or an amide defoamer, and typical but non-limiting examples of the combination are: a combination of a modified silicone oil defoaming agent and a phosphate ester defoaming agent, a combination of a phosphate ester defoaming agent and an amide defoaming agent, a combination of a modified silicone oil defoaming agent and an amide defoaming agent, and the like, preferably a modified silicone oil defoaming agent.
Preferably, the amount of the defoaming agent added is 0.1 to 0.5% by mass of the solid slag, for example, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
The defoaming agent can reduce the foam of a polymerization reaction solution in the concentration and crystallization process, and further can prevent the feed liquid from being entrained into the fraction due to excessive foam. When the concentration and crystallization equipment contains a foam remover such as a foam remover, the defoaming agent can be optionally not added, and the skilled person can reasonably select the concentration and crystallization equipment according to actual conditions.
In a preferred embodiment of the present invention, the amount of water added in step (1) is 2 to 5 times, for example, 2 times, 2.5 times, 3 times, 3.5 times, 4 times, 4.5 times, or 5 times the mass of the solid slag, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the temperature of the dissociation in step (1) is 0 to 100 ℃, for example 0 ℃, 15 ℃, 35 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 60 to 95 ℃.
Preferably, the dissociation time in step (1) is 0.1 to 10 hours, such as 0.1 hour, 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, 3 hours, 5 hours, 7 hours, 9 hours, 10 hours, etc., but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 1 to 3 hours.
As a preferred technical solution of the present invention, the alkali in step (2) is any one or a combination of at least two of calcium oxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium metaaluminate or sodium metaaluminate, and typical but non-limiting examples of the combination are: a combination of calcium oxide and calcium hydroxide, a combination of calcium hydroxide and sodium hydroxide, a combination of sodium hydroxide and potassium hydroxide, a combination of potassium hydroxide and aluminum hydroxide or a combination of calcium metaaluminate and sodium metaaluminate, and the like, preferably calcium oxide and/or calcium hydroxide.
The alkali used for the polymerization reaction is preferably calcium oxide and/or calcium hydroxide, because the calcium oxide and/or calcium hydroxide can not only improve the salinity of the polyaluminium chloride, but also can be used as a phosphorus removing agent to remove phosphorus impurities in the feed liquid.
Preferably, the amount of the alkali added in step (2) is 10-40% of the solid slag, for example, 10%, 20%, 25%, 30%, 35% or 40%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the polymerization reaction in step (2) is carried out at a temperature of 0 to 100 ℃, for example, 0 ℃, 20 ℃, 40 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃, but not limited to the recited values, and other values not recited within the range of the recited values are also applicable, preferably 70 to 95 ℃.
Preferably, the polymerization time in step (2) is 0.1 to 10 hours, such as 0.1 hour, 0.5 hour, 1 hour, 1.2 hour, 1.5 hour, 1.6 hour, 1.8 hour, 2 hour, 4 hour, 6 hour, 8 hour or 10 hour, but not limited to the recited values, and other values within the range are also applicable, preferably 1 to 2 hours.
As a preferable embodiment of the present invention, the polymerization reaction solution in the step (3) is subjected to solid-liquid separation to remove insoluble impurities, and then the concentration and crystallization are carried out; however, when the oxidizing agent is added to the dissociation solution after dissociation, the insoluble impurities in the system are substantially dissolved, and the subsequent concentration and crystallization can be performed without performing solid-liquid separation. Therefore, the person skilled in the art can make a reasonable choice according to the actual situation.
Preferably, the concentration crystallization in the step (3) is concentration crystallization under reduced pressure and/or concentration crystallization under normal pressure.
Preferably, the temperature of the final point of the concentration crystallization in the step (3) is 110 to 120 ℃, for example, 110 ℃, 112 ℃, 114 ℃, 115 ℃, 117 ℃, 119 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the mass of the fraction removed by the concentration and crystallization in the step (3) is 60 to 360% of the mass of the solid slag, for example, 60%, 120%, 180%, 240%, 300%, 360%, etc., but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
The concentrated fraction obtained in the concentration and crystallization process enters a biochemical treatment system, and is discharged after reaching the standard.
As a preferable technical scheme of the invention, the sodium chloride solid in the step (3) is purified.
Preferably, the purification treatment is any one or a combination of at least two of water washing, dissolution, filtration, recrystallization or drying, and the purification treatment is a routine operation in the prior art, and can be reasonably selected by a person skilled in the art according to actual situations.
The sodium chloride solid can be reused for synthesizing the methyl phosphine dichloride after being purified.
In a preferred embodiment of the present invention, the temperature of the aging in the step (4) is 0 to 100 ℃, for example, 0 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 60 ℃, 80 ℃ or 100 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable, preferably 10 to 40 ℃.
Preferably, the curing time in the step (4) is 1 to 100 hours, such as 1 hour, 12 hours, 24 hours, 30 hours, 36 hours, 42 hours, 48 hours, 60 hours, 70 hours, 80 hours, 90 hours or 100 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 24 to 48 hours.
As a preferred technical solution of the present invention, the processing method comprises the steps of:
(1) mixing the tetrachloro sodium aluminate solid slag with water, dissociating for 0.1-10 h at 0-100 ℃, and adding an oxidant for oxidation;
wherein the addition amount of the water is 2-5 times of the mass of the solid slag, and the addition amount of the oxidant is 1-50% of the mass of the solid slag;
(2) adding alkali into the dissociation solution obtained in the step (1) to carry out polymerization reaction, and carrying out polymerization reaction for 0.1-10 h at 0-100 ℃ to obtain a polymerization reaction solution;
wherein the addition amount of the alkali is 10-40% of the mass of the solid slag;
(3) carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2), removing insoluble impurities, then adding a defoaming agent, and then carrying out concentration crystallization and solid-liquid separation to obtain sodium chloride solid and concentrated mother liquor;
wherein the addition amount of the defoaming agent is 0.1-0.5% of the mass of the solid slag, the final temperature of the concentration crystallization is 110-120 ℃, and the mass of the fraction removed by the concentration crystallization is 60-360% of the mass of the solid slag;
(4) curing the concentrated mother liquor obtained in the step (3) at 0-100 ℃ for 1-100 h to obtain a poly (aluminum chloride) liquid product.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) after the dissociation of the tetrachloro sodium aluminate solid slag, firstly adding alkali to carry out the polymerization reaction of aluminum chloride, then obtaining sodium chloride solid through concentration and crystallization, and then curing the concentrated mother liquor to obtain a polymerized aluminum chloride liquid product, namely Al2O3The mass fraction is more than or equal to 10 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB 15892-2009 are met; moreover, the removal rate of the polymerized aluminum chloride liquid product on the waste water reaches the effect of a commercial product, and the removal rate of the turbidity is more than or equal to 90 percent and can reach 97.28 percent at most;
(2) the treatment method of the invention can not only further dry the liquid product of the polyaluminum chloride obtained by curing to obtain the solid product of the polyaluminum chloride, Al2O3The mass fraction is more than or equal to 28.0 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB/T22627-2014 are met; or adding ferric trichloride for curing before curing the concentrated mother liquor to obtain a polyaluminum ferric chloride liquid product, Al2O3The mass fraction of the iron is more than or equal to 9 percent, the mass fraction of the total iron (Fe) is more than or equal to 2 percent, the basicity is more than or equal to 60 percent, and the index requirements of the chemical industry standard HG/T5359-2018 are met;
(3) the treatment method not only solves the problem of solid waste disposal, but also prepares a high value-added polyaluminum chloride liquid product, does not need to introduce an organic solvent, does not have cross contamination, and can reduce the cost;
(4) the treatment method has the advantages of simple process flow, simple and convenient operation, less equipment investment and the like, and is suitable for large-scale industrial popularization.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a method for processing tetrachloro sodium aluminate solid slag, wherein the tetrachloro sodium aluminate solid slag is obtained in a production process of synthesizing diethyl methylphosphonite by taking phosphorus trichloride, methyl chloride, aluminum trichloride, aluminum powder, sodium chloride and the like as raw materials, the content of tetrachloro sodium aluminate in the solid slag is 95%, and the processing method comprises the following steps:
(1) mixing 100g of solid residue with the content of sodium tetrachloroaluminate of 95% with 300g of water, dissociating for 1.5h at 80 ℃, adding 5g of sodium chlorate serving as an oxidant, and oxidizing for 1h at 90 ℃;
(2) adding 40g of 96% sodium hydroxide solid into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 1h at 80 ℃;
(3) sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation on the polymerization reaction solution obtained in the step (2) at the end point temperature of 114 ℃ to obtain 120g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 120g of sodium chloride solid is washed by 100g of water, and then dried to obtain 80g of sodium chloride product which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) curing 170g of the concentrated mother liquor obtained in the step (3) at 30 ℃ for 36h to obtain 170g of a poly aluminum chloride liquid product.
Example 2
The embodiment provides a method for treating tetrachloro sodium aluminate solid slag, which is the same as that in embodiment 1, and comprises the following steps:
(1) mixing 100g of solid residue with the content of sodium tetrachloroaluminate of 95% with 500g of water, dissociating for 1h at 90 ℃, adding 5g of sodium chlorate serving as an oxidant, and oxidizing for 1h at 90 ℃;
(2) adding 40g of 96% sodium hydroxide solid into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 1h at 95 ℃;
(3) sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation on the polymerization reaction solution obtained in the step (2) at the end point temperature of 114 ℃ to obtain 120g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 120g of sodium chloride solid is washed by 100g of water, and then dried to obtain 80g of sodium chloride product which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) and (3) curing 170g of the concentrated mother liquor obtained in the step (3) at 40 ℃ for 24h, and then removing water by thin film evaporation to obtain 60g of a polyaluminum chloride solid product.
Example 3
The embodiment provides a method for treating tetrachloro sodium aluminate solid slag, which is the same as that in embodiment 1, and comprises the following steps:
(1) mixing 100g of solid slag containing 95% of sodium tetrachloroaluminate with 400g of water, dissociating for 3h at 60 ℃, adding 50g of oxydol serving as an oxidant, and oxidizing for 1h at 60 ℃;
(2) adding 100g of sodium hydroxide solution with the content of 40% into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 2h at 70 ℃;
(3) sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation on the polymerization reaction solution obtained in the step (2) at the end point temperature of 114 ℃ to obtain 120g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 120g of sodium chloride solid is washed by 100g of water, and then dried to obtain 80g of sodium chloride product which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) and (3) curing 170g of the concentrated mother liquor obtained in the step (3) at 10 ℃ for 48h, and then removing water by spray drying to obtain 60g of a polyaluminum chloride solid product.
Example 4
The embodiment provides a method for treating tetrachloro sodium aluminate solid slag, which is the same as that in embodiment 1, and comprises the following steps:
(1) mixing 100g of solid residue with the content of sodium tetrachloroaluminate of 95% with 400g of water, dissociating for 0.5h at 95 ℃, adding 5g of sodium chlorate serving as an oxidant, and oxidizing for 1h at 90 ℃;
(2) adding 60g of potassium hydroxide solution with the content of 90% into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 5h at 25 ℃;
(3) sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation on the polymerization reaction solution obtained in the step (2) at the end temperature of 112 ℃ to obtain 70g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 70g of sodium chloride solid is washed by 50g of water, and then 32g of sodium chloride product is obtained by drying, which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) curing 170g of the concentrated mother liquor obtained in the step (3) at 40 ℃ for 48h to obtain 170g of a poly aluminum chloride liquid product.
Example 5
The embodiment provides a method for treating tetrachloro sodium aluminate solid slag, which is the same as that in embodiment 1, and comprises the following steps:
(1) mixing 100g of solid slag with the content of sodium tetrachloroaluminate of 95% with 400g of water, and dissociating for 0.5h at 100 ℃;
(2) adding 25g of calcium oxide into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 2h at 90 ℃;
(3) carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2), removing 1g of insoluble impurities, then adding 0.1g of modified silicone oil 8750 antifoaming agent, and then sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation at the end temperature of 118 ℃ to obtain 70g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 70g of sodium chloride solid is washed by 50g of water, and then 32g of sodium chloride product is obtained by drying, which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) and (4) curing 170g of the concentrated mother liquor obtained in the step (3) at 30 ℃ for 24h to obtain 170g of a poly-aluminum chloride liquid product.
Example 6
The embodiment provides a method for treating tetrachloro sodium aluminate solid slag, which is the same as that in embodiment 1, and comprises the following steps:
(1) mixing 100g of solid slag containing 95% of sodium tetrachloroaluminate with 400g of water, and dissociating for 1h at 95 ℃;
(2) adding 33g of calcium hydroxide into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 2h at 95 ℃;
(3) carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2), removing 1g of insoluble impurities, then adding 0.05g of modified silicone oil 8750 antifoaming agent, and then sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation at the end temperature of 118 ℃ to obtain 70g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 70g of sodium chloride solid is washed by 50g of water, and then 32g of sodium chloride product is obtained by drying, which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) curing 170g of the concentrated mother liquor obtained in the step (3) at 10 ℃ for 48h to obtain 170g of a poly aluminum chloride liquid product.
Example 7
The embodiment provides a method for treating tetrachloro sodium aluminate solid slag, which is the same as that in embodiment 1, and comprises the following steps:
(1) mixing 100g of solid slag containing 95% of sodium tetrachloroaluminate with 400g of water, and dissociating at 80 ℃ for 10 hours;
(2) adding 60g of potassium hydroxide into the dissociation solution obtained in the step (1), and carrying out polymerization reaction for 1h at 80 ℃;
(3) carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2), removing 1g of insoluble impurities, then adding 0.1g of modified silicone oil 8750 antifoaming agent, and then sequentially carrying out normal-pressure concentration crystallization and solid-liquid separation at the end temperature of 112 ℃ to obtain 70g of sodium chloride solid and 170g of concentrated mother liquor;
wherein, 70g of sodium chloride solid is washed by 50g of water, and then 32g of sodium chloride product is obtained by drying, which can be reused for the synthesis of the methyl phosphine dichloride, and the washing brine is poured into the polymerization reaction solution of the next batch for concentration and crystallization; concentrated fractions obtained in the process of concentration and crystallization enter a biochemical treatment system, and are discharged after reaching the standard;
(4) adding 170g of concentrated mother liquor obtained in the step (3) into 21g of ferric trichloride, curing at 90 ℃ for 3h, and removing 15g of precipitate through solid-liquid separation to obtain 176g of polymeric aluminum ferric chloride liquid product.
Comparative example 1
Commercially available Al2O310% of a polyaluminum chloride liquid product (quanzhou sandiskei chemical limited, first-class product, type: PAC) was used as a control product A.
And (3) performance testing:
the polyaluminum chloride products obtained in examples 1 to 6, the polyaluminum ferric chloride liquid product obtained in example 7, and the control product a described in comparative example 1 were subjected to the following tests:
for the polyaluminium chloride product, Al is subjected to a test method disclosed in national standard GB/T22627-2O3The mass fraction and basicity of (a);
for the polyaluminum ferric chloride liquid product, Al is subjected to a test method disclosed in chemical industry standard HG/T5359-2018 water treatment agent polyaluminum ferric chloride2O3The mass fraction of (a), the basicity and the mass fraction of total iron (Fe) are measured;
the specific test results are shown in table 1.
TABLE 1
The poly aluminum chloride liquid product obtained in the example 6 is compared with the control product A in the comparative example 1 in terms of wastewater treatment effect, the turbidity removal rate is used as an evaluation index, and wastewater (the turbidity 500) of a certain batch of the Xinan chemical glyphosate plant in Zhejiang is used as an actual wastewater sample. The turbidity removal rate test method comprises the following steps: two kinds of polyaluminium chloride are put into an actual wastewater sample, the adding amount is controlled to be 12.5mg/L, 25mg/L, 37.5mg/L, 50mg/L, 62.5mg/L and 75mg/L respectively, turbidity before and after the actual wastewater sample is treated is measured by a turbidimeter respectively, and then the calculation is carried out by a formula. The specific test results are shown in table 2.
TABLE 2
As can be seen from Table 2, under the condition of low adding amount of polyaluminium chloride, the turbidity removal rate of the polyaluminium chloride liquid product obtained in the embodiment 6 of the invention and the turbidity removal rate of the contrast product A purchased in the market in the comparative example 1 are basically consistent and can reach more than 90%; moreover, the turbidity removal rate of the polyaluminium chloride and the turbidity removal rate of the polyaluminium chloride to waste water are both gradually improved with the increase of the adding amount of the polyaluminium chloride, and the maximum turbidity removal rate can reach 97.28%.
In summary, the following points can be obtained:
(1) after the dissociation of the tetrachloro sodium aluminate solid slag, the treatment method firstly adds alkali for chlorinePolymerizing the aluminum, concentrating and crystallizing to obtain sodium chloride solid, and curing the concentrated mother liquor to obtain the polyaluminum chloride liquid product Al2O3The mass fraction is more than or equal to 10 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB 15892-2009 are met;
(2) in the embodiments 2 and 3 of the invention, the polyaluminum chloride liquid product obtained by curing is further dried to obtain a polyaluminum chloride solid product, Al2O3The mass fraction is more than or equal to 28.0 percent, the basicity is more than or equal to 60 percent, and the index requirements of the national standard GB/T22627-2014 are met;
(3) in the embodiment 7 of the invention, before the concentrated mother liquor is cured, ferric trichloride is added for curing to obtain a polyaluminum ferric chloride liquid product, Al2O3The mass fraction of the iron is more than or equal to 9 percent, the mass fraction of the total iron (Fe) is more than or equal to 2 percent, the basicity is more than or equal to 60 percent, and the index requirements of the chemical industry standard HG/T5359-2018 are met;
(4) the treatment method not only solves the problem of solid waste disposal, but also prepares and obtains a high value-added polymerized aluminum chloride liquid product, does not need to introduce an organic solvent, does not have cross contamination, can reduce the cost, has the advantages of simple process flow, simple and convenient operation, less equipment investment and the like, and is suitable for large-scale industrial popularization.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (36)
1. A method for treating tetrachloro sodium aluminate solid slag is characterized by comprising the following steps:
(1) mixing the tetrachloro sodium aluminate solid slag with water for dissociation, wherein the addition amount of the water is 2-5 times of the mass of the solid slag, so as to obtain a dissociation solution;
(2) adding alkali into the dissociation solution obtained in the step (1) to carry out polymerization reaction to obtain a polymerization reaction solution;
(3) concentrating, crystallizing and carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2) to obtain sodium chloride solid and concentrated mother liquor;
(4) curing the concentrated mother liquor obtained in the step (3) to obtain a poly aluminum chloride liquid product.
2. The process of claim 1, wherein the polyaluminum chloride liquid product of step (4) is dried to obtain a polyaluminum chloride solid product.
3. The process according to claim 2, characterized in that the drying is spray drying and/or thin film evaporation.
4. The process of claim 1, wherein ferric chloride is added to the concentrated mother liquor of step (4), and then the aging is performed to obtain polyaluminum ferric chloride liquid product.
5. The process according to claim 4, wherein the temperature of the aging is 10 to 40 ℃.
6. The treatment method according to claim 4, wherein the curing time is 24-48 h.
7. The treatment method according to claim 1, wherein an oxidizing agent is added to the dissociation solution of step (1) to perform oxidation.
8. The treatment method according to claim 7, wherein the oxidant is any one or a combination of at least two of sodium chlorate, hydrogen peroxide, manganese dioxide, nitric acid, ferric chloride and ozone.
9. The process according to claim 8, characterized in that said oxidizing agent is sodium chlorate and/or hydrogen peroxide.
10. The treatment method according to claim 7, wherein the amount of the oxidant added is 1-50% by mass of the solid slag.
11. The process according to claim 1, wherein an antifoaming agent is added to the polymerization reaction solution in the step (3).
12. The method according to claim 11, wherein the defoaming agent is any one of a modified silicone oil defoaming agent, a phosphate ester defoaming agent, or an amide defoaming agent, or a combination of at least two of them.
13. The method of claim 12, wherein the defoamer is a modified silicone oil defoamer.
14. The treatment method according to claim 11, wherein the amount of the antifoaming agent added is 0.1 to 0.5% by mass of the solid slag.
15. The process of claim 1, wherein the temperature of the dissociation in step (1) is 0 to 100 ℃.
16. The process of claim 15, wherein the temperature of the dissociation in step (1) is 60 to 95 ℃.
17. The treatment method according to claim 1, wherein the dissociation time in step (1) is 0.1-10 h.
18. The process of claim 17, wherein the dissociation time in step (1) is 1-3 h.
19. The process of claim 1, wherein the alkali in step (2) is any one or a combination of at least two of calcium oxide, calcium hydroxide, sodium hydroxide, potassium hydroxide, aluminum hydroxide, calcium metaaluminate or sodium metaaluminate.
20. The process of claim 19, wherein the base of step (2) is calcium oxide and/or calcium hydroxide.
21. The treatment method according to claim 1, wherein the alkali is added in the step (2) in an amount of 10 to 40% by mass of the solid slag.
22. The process according to claim 1, wherein the polymerization reaction in the step (2) is carried out at a temperature of 0 to 100 ℃.
23. The process according to claim 22, wherein the polymerization reaction in the step (2) is carried out at a temperature of 70 to 95 ℃.
24. The process according to claim 1, wherein the polymerization reaction time in step (2) is 0.1 to 10 hours.
25. The process of claim 24, wherein the polymerization reaction time in step (2) is 1-2 hours.
26. The method according to claim 1, wherein the polymerization reaction solution in the step (3) is subjected to solid-liquid separation to remove insoluble impurities, and then the concentration and crystallization are carried out.
27. The treatment method according to claim 1, wherein the concentration crystallization in the step (3) is concentration crystallization under reduced pressure and/or concentration crystallization under normal pressure.
28. The process according to claim 1, wherein the final temperature of the concentration crystallization in the step (3) is 110 to 120 ℃.
29. The treatment method according to claim 1, wherein the mass of the fraction removed by the concentration and crystallization in the step (3) is 60-360% of the mass of the solid slag.
30. The process according to claim 1, characterized in that said sodium chloride solid of step (3) is subjected to a purification treatment.
31. The process of claim 30, wherein the purification treatment is any one or a combination of at least two of water washing, dissolution, filtration, recrystallization, or drying.
32. The process according to claim 1, wherein the temperature of the aging in the step (4) is 0 to 100 ℃.
33. The process of claim 32, wherein the curing temperature in step (4) is 10 to 40 ℃.
34. The treatment method according to claim 1, wherein the curing time in the step (4) is 1-100 h.
35. The process of claim 34, wherein the aging time in step (4) is 24 to 48 hours.
36. The processing method according to claim 1, characterized in that it comprises the steps of:
(1) mixing the tetrachloro sodium aluminate solid slag with water, dissociating for 0.1-10 h at 0-100 ℃, and adding an oxidant for oxidation;
wherein the addition amount of the water is 2-5 times of the mass of the solid slag, and the addition amount of the oxidant is 1-50% of the mass of the solid slag;
(2) adding alkali into the dissociation solution obtained in the step (1) to carry out polymerization reaction, and carrying out polymerization reaction for 0.1-10 h at 0-100 ℃ to obtain a polymerization reaction solution;
wherein the addition amount of the alkali is 10-40% of the mass of the solid slag;
(3) carrying out solid-liquid separation on the polymerization reaction solution obtained in the step (2), removing insoluble impurities, then adding a defoaming agent, and then carrying out concentration crystallization and solid-liquid separation to obtain sodium chloride solid and concentrated mother liquor;
wherein the addition amount of the defoaming agent is 0.1-0.5% of the mass of the solid slag, the final temperature of the concentration crystallization is 110-120 ℃, and the mass of the fraction removed by the concentration crystallization is 60-360% of the mass of the solid slag;
(4) curing the concentrated mother liquor obtained in the step (3) at 0-100 ℃ for 1-100 h to obtain a poly (aluminum chloride) liquid product.
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